US10174139B2 - Crosslinker-accelerator system for polyacrylates - Google Patents

Crosslinker-accelerator system for polyacrylates Download PDF

Info

Publication number
US10174139B2
US10174139B2 US13/745,298 US201313745298A US10174139B2 US 10174139 B2 US10174139 B2 US 10174139B2 US 201313745298 A US201313745298 A US 201313745298A US 10174139 B2 US10174139 B2 US 10174139B2
Authority
US
United States
Prior art keywords
crosslinker
accelerator
crosslinking
groups
polyacrylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US13/745,298
Other languages
English (en)
Other versions
US20130190460A1 (en
Inventor
Alexander Prenzel
Sarah Bamberg
Jennifer Beschmann
Marten Papenbroock
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tesa SE
Original Assignee
Tesa SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tesa SE filed Critical Tesa SE
Assigned to TESA SE reassignment TESA SE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: Beschmann, Jennifer, PAPENBROOCK, MARTEN, Bamberg, Sarah, PRENZEL, ALEXANDER, DR
Publication of US20130190460A1 publication Critical patent/US20130190460A1/en
Assigned to TESA SE reassignment TESA SE CHANGE OF ADDRESS Assignors: TESA SE
Application granted granted Critical
Publication of US10174139B2 publication Critical patent/US10174139B2/en
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C08F2220/1825—
    • C08F2220/1858—

Definitions

  • the present invention relates to the technical field of crosslinkable polyacrylates.
  • a system is proposed for controlling the crosslinking rate of thermally crosslinkable polyacrylates, this system being based on the combination of a substance containing epoxide groups with a specifically substituted amine.
  • Polyacrylates are widely used for high-grade industrial applications, as adhesives, more particularly as pressure-sensitive adhesives or heat-sealing adhesives, having proved to be highly suitable for the growing requirements in these areas of application.
  • pressure-sensitive adhesives PSAs
  • PSAs pressure-sensitive adhesives
  • these compositions must be suitable for coating onto carrier materials. All of this can be achieved through the use of polyacrylates with a high molecular weight and high polarity, and their efficient crosslinking.
  • polyacrylates can be produced to be transparent and stable to weathering.
  • thermal crosslinking For the coating of polyacrylate compositions useful as PSA from solution or as a dispersion, thermal crosslinking has long been state of the art.
  • the thermal crosslinker for example a polyfunctional isocyanate, a metal chelate or a polyfunctional epoxide—is added to the solution or dispersion of a polyacrylate equipped with corresponding functional groups, the resulting composition is coated as a sheetlike film onto a substrate, and the coating is subsequently dried.
  • organic solvents, or water in the case of dispersions are evaporated, and the polyacrylate, accordingly, is crosslinked.
  • Crosslinking is very important for the coatings, since it gives them sufficient cohesion and thermal shear strength.
  • the coatings would be too soft and would flow away under even a low load.
  • Critical to a good coating outcome is the observance of the potlife (processing life, within which the system is in a processible state), which can vary greatly according to crosslinking system. If this life is too short, the crosslinker has already undergone reaction in the polyacrylate solution; the solution is already partly crosslinked and can no longer be applied uniformly.
  • melt processes also referred to as hotmelt processes
  • solvent-free coating technology for the production of PSAs.
  • meltable polymer compositions i.e. polymer compositions which at elevated temperatures enter into the fluid state without decomposing, are processed.
  • Such compositions can be processed outstandingly from the melt state.
  • an aim is to make the production of the product compositions as well a low-solvent or solvent-free operation.
  • the pressure-sensitive adhesive layer must be relatively thin in order for well-crosslinked layers to be obtainable by chemical radiation methods.
  • the thickness through which radiation can pass though indeed varying as a function of density, accelerator voltage (EBC) and/or active wavelength (UV), is always greatly limited; accordingly, it is not possible to effect crosslinking through layers of arbitrary thickness, and certainly not homogeneously.
  • DE 10 2004 044 086 A1 describes a process for the thermal crosslinking of acrylate hotmelts that coats a solvent-free functionalized acrylate copolymer, which following metered addition of a thermally reactive crosslinker has a processing life that is long enough for compounding, conveying and coating, onto a web-form layer of a further material and then crosslinks this coating under mild conditions until the cohesion achieved is sufficient for pressure-sensitive adhesive tapes.
  • a disadvantage of this process is that the reactivity of the crosslinker (isocyanate) predetermines the free processing life and the degree of crosslinking. Isocyanate crosslinkers react in some cases even during their addition; consequently, depending on the system, the gel-free time can be very short.
  • a composition with a sizable fraction of functional groups such as hydroxyl groups or carboxylic acid can in that case no longer be applied sufficiently well.
  • a streaky coat interspersed with gel specks and hence inhomogeneous would be the result.
  • Another problem which arises is that the achievable degree of crosslinking is limited. If a higher degree of crosslinking through addition of a higher quantity of crosslinker is desired, this has disadvantages when polyfunctional isocyanates are used.
  • the composition would react too quickly and would be coatable, if at all, only with a very short processing life and hence at very high coating speeds, which would exacerbate the problems of the non-homogeneous coating appearance.
  • Epoxides react fundamentally only under the influence of heat, and more particularly only after prolonged supply of thermal energy.
  • Known accelerator substances such as ZnCl 2 , for example, do lead to an improvement in the reaction capacity within the temperature range of polymer melts, but in the absence of a supply of thermal energy from the outside (in other words, for example, at room temperature), the reactivity of the epoxides is lost, even in the presence of the accelerators, and so the crosslinking reaction breaks down (in other words, at the prevailing temperature, the accelerators no longer have an accelerating activity).
  • crosslinker system with only thermally functioning accelerators, such as ZnCl 2 , were to be introduced too early into the polyacrylate system (in order to achieve a sufficient degree of crosslinking), then the compositions would no longer be able to be homogeneously processed, more particularly compounded and coated, since they would crosslink too quickly or would even “gel” (undergo uncontrolled crosslinking). If, on the other hand, the accelerator causes too little activation of epoxide crosslinking, then a very long secondary crosslinking time can be expected or the compositions will have to be stored at high temperatures, which is undesirable.
  • accelerators such as ZnCl 2
  • a further problem is that certain accelerator substances result in an increase in the melt viscosity.
  • polyacrylate hotmelts polyacrylate compositions which can be processed from the melt
  • potlife a sufficiently long processing life
  • the intention is that it should be possible to set the degree of crosslinking of the polyacrylate composition to a desired level, without adversely affecting the advantages of the operating regime. More particularly, any increase in viscosity of the composition after addition of the accelerator is to be avoided as far as possible. Even at low temperatures, the secondary crosslinking is to proceed rapidly to an end level.
  • polyacrylate compositions are also referred to synonymously for short as “polyacrylates”.
  • polyacrylates for the noncrosslinked polyacrylate compositions, the term “polymerisates” is also used, while the term “polymers” is used for the fully or partly crosslinked polyacrylate compositions.
  • a first subject of the invention is a crosslinker-accelerator system for the thermal crosslinking of polyacrylates having functional groups suitable for entering into linking reactions with epoxide groups, comprising
  • the radicals R independently of one another are a hydrogen atom or an organic radical with 1 to 20 carbon atoms, with at least one of the radicals R being an organic radical with 1 to 20 carbon atoms and comprising at least one alcoholic OH group.
  • a crosslinker-accelerator system of this kind enables, initially, comfortable processing lives for the polyacrylate compositions, while later a speedy secondary crosslinking is ensured even at low temperatures, more particularly at room temperature.
  • the crosslinker-accelerator system of the invention avoids the above-recited disadvantages of conventional crosslinking systems, and is custom-tailored to the requirements of an industrially implemented operation for producing PSAs or PSA-coated products.
  • thermo crosslinking process which when applied to the processing of polyacrylate hotmelt compositions does not lead to uncontrolled reactions (gelling of the composition) and leaves a sufficiently long time for processing (potlife), thus making it possible in particular to achieve a uniform and blister-free coating when the composition is coated out as a layer or is applied to a carrier.
  • a very advantageous effect of the crosslinker-accelerator system of the invention is that the necessary secondary crosslinking of the polyacrylate composition after processing, more particularly after being coated out as a layer or applied to a carrier, proceeds rapidly, with a supply of thermal energy reduced significantly by comparison with melt production, in other words after cooling, without any need for actinic irradiation for this purpose.
  • rapid crosslinking is meant that the elastic fraction of the composition, measured by means of microshear travel method H3, is significantly more than 25%, more preferably more than 35%, within a week.
  • the polyacrylates are capable of undergoing further crosslinking without further thermal energy (heating) supplied actively—that is, by technical process means—more particularly after cooling to room temperature (RT, 20° C.) or to a temperature close to room temperature. More particularly it is possible in this crosslinking phase to do without heating, without this leading to a termination of the crosslinking reaction.
  • thermal energy heat supplied actively—that is, by technical process means—more particularly after cooling to room temperature (RT, 20° C.) or to a temperature close to room temperature. More particularly it is possible in this crosslinking phase to do without heating, without this leading to a termination of the crosslinking reaction.
  • a “crosslinker” for the purposes of the invention is a substance via which the polyacrylate molecules are linked to form three-dimensional structures by formation of covalent bonds.
  • An “accelerator” is a substance which supports the crosslinking reaction by ensuring a significantly increased crosslinking reaction rate in comparison to the absence of the accelerator. This is true, of course, in the case of comparable reaction parameters and more particularly at temperatures below the melting temperature of the polyacrylates. Within this temperature range, the crosslinking reaction without accelerators would not proceed at all or would proceed only very slowly. The accelerator, then, produces a substantial improvement in the reaction kinetics of the crosslinking reaction. In accordance with the invention this can be done catalytically, but also by incorporation into the reaction event.
  • Polyacrylates are polymers whose monomer basis, in terms of amount of substance, consists to an extent of at least 30% of acrylic acid, methacrylic acid, acrylic esters and/or methacrylic esters, with acrylic esters and/or methacrylic esters being present at least proportionally, generally and preferably to an extent of at least 30%. More particularly, a “polyacrylate” is a polymerisate which is obtainable by radical polymerization of acrylic and/or methylacrylic monomers and also, optionally, further, copolymerisable monomers.
  • the crosslinker-accelerator system of the invention comprises at least one substance which contains at least one epoxide group as crosslinker.
  • Substances containing epoxide groups that are used are preferably polyfunctional epoxides, these being those which have at least two epoxide functions per molecule (i.e. are at least difunctional in respect of the epoxide groups). They may be either aromatic or aliphatic compounds.
  • suitable polyfunctional epoxides are oligomers of epichlorohydrin, epoxy ethers of polyhydric alcohols (more particularly ethylene, propylene and butylene glycols, polyglycols, thiodiglycols, glycerol, pentaerythritol, sorbitol, polyvinyl alcohol, polyallyl alcohol and the like); epoxy ethers of polyhydric phenols (more particularly resorcinol, hydroquinone, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, bis(4-hydroxy-3,5-difluorophenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy
  • ethers containing epoxide groups examples include 1,4-butanediol diglycidyl ether, polyglycerol-3 glycidyl ether, cyclohexanedimethanol diglycidyl ether, glycerol triglycidyl ether, neopentyl glycol diglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexanediol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A diglycidyl ether and bisphenol F diglycidyl ether.
  • the crosslinker-accelerator system of the invention further comprises at least one substance conforming to the general formula (I) NR 3 (I), in which the radicals R independently of one another are a hydrogen atom or an organic radical having 1 to 20 carbon atoms, where at least one of the radicals R is an organic radical having 1 to 20 carbon atoms, and comprises at least one alcoholic OH group, as accelerator.
  • the radicals R independently of one another are a hydrogen atom or an organic radical having 1 to 20 carbon atoms, where at least one of the radicals R is an organic radical having 1 to 20 carbon atoms, and comprises at least one alcoholic OH group, as accelerator.
  • At least two radicals R independently of one another are an organic radical having 1 to 20 carbon atoms, with at least one of these radicals R comprising at least one alcoholic OH group. More preferably all three radicals R independently of one another are an organic radical having 1 to 20 carbon atoms, with at least one of the radicals R comprising at least one alcoholic OH group.
  • At least one of the radicals R is a hydroxyalkyl group having 1 to 8 carbon atoms. Likewise preferably all three radicals R are substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms.
  • substituted is meant that a hydrogen atom which is bonded to a carbon atom belonging to the respective radical is replaced by another atom or by a chemical group, such as a functional group, for example, where the group atom bonded directly to the relevant carbon atom of the radical may in particular also be a heteroatom, in other words not a carbon atom.
  • substituted alkyl radical covers radicals which in spite of substitution can still be identified as alkyl radicals in terms of their essential nature. These include, for example, radicals that are hydroxylated or halogenated in position 1, in other words on the carbon atom bonded directly to the nitrogen atom.
  • substituted alkyl radical are radicals, for example, whose carbon atom in position 1 is part of a carbonyl group or of a comparable functional group, which no longer allows the radical in question to be classed, in terms of its essential nature, among the alkyl radicals.
  • At least one of the radicals R is a hydroxyalkyl group having 1 to 8 carbon atoms, and at least one further radical R is an aminoalkyl group having 1 to 8 carbon atoms.
  • a particular advantage of the crosslinker-accelerator system of the invention is that the rise in melt viscosity induced by the amino alcohol accelerator of the invention is smaller than in the case, for example, of pure amine accelerators having the same number of activating groups. This means that the energy input or heat input needed in the extrusion operation becomes smaller, and hence also the crosslinking of the polyacrylate in the processing operation is slowed down. As a result, longer potlives or further-processing lives are available.
  • the ratio of the number of hydroxyl groups to the number of amino functionalities per accelerator molecule is from 0.33 to 1.
  • the higher the number of hydroxyl groups per accelerator molecule the greater the reduction in the melt viscosity by comparison with, for example, a pure amine accelerator having the same number of amine functionalities.
  • amino groups or “amino functionalities” refers in accordance with the invention both to —NH 2 groups and to secondary and tertiary amino groups, in which one or both hydrogen atoms are substituted, particularly by substituted or unsubstituted alkyl groups.
  • the substance conforming to the general formula (I) preferably contains exclusively secondary, more preferably exclusively tertiary, amino functionalities, more particularly those having exclusively methyl and/or ethyl substituents, and very preferably those having exclusively methyl substituents.
  • Suitable substances conforming to the general formula (I) are, for example, 2,2-(di-tert-butylphosphino)ethylamine, 2,2-(diisopropylphosphino)ethylamine, 2,2-(diphenyl-phosphino)ethylamine, N-(3-dimethylaminopropyl)-N,N-diisopropanolamine, (1R,2R)-2-(benzyloxy)cyclohexylamine and (1S,2S)-2-(benzyloxy)cyclohexylamine, N,N-di-methylethanolamine, bis(2-dimethylaminoethyl)ether, N,N,N′-trimethyl-N′-hydroxyethylbisaminoethyl ether, 2-(2-dimethylaminoethoxy)ethanol, N,N,N′-trimethylaminoethyl-ethanolamine, 2,2′-dimorpholino
  • a further subject of the present invention is a thermally crosslinkable composition which comprises at least one polyacrylate having functional groups suitable for entering into linking reactions with epoxide groups, and a crosslinker-accelerator system of the invention.
  • This is more particularly a thermally crosslinkable composition which comprises at least one polyacrylate having functional groups which are suitable for entering into linking reactions of epoxide groups, and
  • crosslinker at least one substance which comprises at least one epoxide group (crosslinker), and
  • radicals R independently of one another are a hydrogen atom or an organic radical having 1 to 20 carbon atoms, where at least one of the radicals R is an organic radical having 1 to 20 carbon atoms, and at least one alcoholic OH group.
  • the total fraction of substances which comprise at least one epoxide group is preferably 0.1%-5% by weight, more preferably 0.15%-0.4% by weight, based on the pure (without additives) polyacrylate to be crosslinked.
  • the total fraction of accelerator is preferably 0.05%-5% by weight, more preferably 0.1%-1.2% by weight, based on the additive-free polyacrylate to be crosslinked.
  • “Pure polyacrylate to be crosslinked” means in accordance with the invention “only the polyacrylate to be crosslinked, without any additives”. It is particularly advantageous if the crosslinker fraction is selected so as to result in an elastic fraction of the crosslinked polyacrylates of at least 20%.
  • the elastic fraction is preferably at least 40%, more preferably at least 60% (measured in each case by measurement method H3; cf. Experimental Section).
  • monomers or comonomers for preparing the polyacrylate it is preferred, accordingly, to make proportional use of functional monomers which are crosslinkable with epoxide groups.
  • functional monomers which are crosslinkable with epoxide groups.
  • These are preferably monomers with acid groups (particularly carboxylic acid, sulphonic acid or phosphonic acid groups) and/or hydroxyl groups and/or acid anhydride groups and/or epoxide groups and/or amine groups; monomers containing carboxylic acid groups are particularly preferred.
  • the polyacrylate comprises copolymerized acrylic acid and/or methacrylic acid.
  • Further monomers which may be used as comonomers for the polyacrylate, besides acrylic and/or methacrylic esters having up to 30 C atoms, are, for example, vinyl esters of carboxylic acids comprising up to 20 C atoms, vinylaromatics having up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols comprising 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C atoms and 1 or 2 double bonds, or mixtures of these monomers.
  • the properties of the polyacrylate may be influenced in particular by varying the glass transition temperature of the polymer, by means of different weight fractions of the individual monomers.
  • Amorphous or semi-crystalline systems are characterized by the transformation of the more or less hard amorphous or semi-crystalline phase into a softer (rubberlike to viscous) phase.
  • thawing or “freezing” in the case of cooling
  • the transition from the melting point T m (also “melting temperature”; really defined only for purely crystalline systems; “polymer crystals”) to the glass transition point T g (also “glass transition temperature”, “glass temperature”) can therefore be considered to be a fluid transition, depending on the proportion of semi-crystallinity in the sample under analysis.
  • the reference for the purposes of this specification includes the melting point as well—in other words, the glass transition point (or else, synonymously, the glass transition temperature) is also understood to include the melting point for the corresponding “melting” systems.
  • the statements of the glass transition temperatures relate to the determination by means of dynamic mechanical analysis (DMA) at low frequencies.
  • the quantitative composition of the monomer mixture is advantageously selected such that, in accordance with an equation (E1) in analogy to the Fox equation (cf. T. G. Fox, Bull. Am. Phys. Soc. 1956, 1, 123), the desired T g value for the polymer is produced.
  • n represents the serial number of the monomers used
  • w n represents the mass fraction of the respective monomer n (% by weight)
  • T g,n represents the respective glass transition temperature of the homopolymer of each of the monomers n, in K.
  • the fractions of the corresponding components (a), (b) and (c) are selected such that the polymerization product more particularly has a glass transition temperature ⁇ 15° C. (DMA at low frequencies).
  • the monomers of component (a) with a fraction from 45% to 99% by weight, the monomers of component (b) with a fraction from 1% to 15% by weight and the monomers of component (c) with a fraction from 0% to 40% by weight (the figures are based on the monomer mixture for the “base polymer”, i.e. without additions of any additives to the completed polymer, such as resins etc.).
  • the fractions of components (a), (b), and (c) are selected more particularly such that the copolymer has a glass transition temperature (T g ) of between 15° C. and 100° C., preferably between 30° C. and 80° C., more preferably between 40° C. and 60° C.
  • T g glass transition temperature
  • a viscoelastic material which may typically be laminated on both sides with pressure-sensitive adhesive layers, has a glass transition temperature (T g ) in particular of between ⁇ 50° C. to +100° C., preferably between ⁇ 20° C. to +60° C., more preferably 0° C. to 40° C.
  • T g glass transition temperature
  • the fractions of components (a), (b) and (c) should be selected accordingly.
  • the monomers of component (a) are, in particular, plasticizing and/or apolar monomers.
  • monomers (a) it is preferred to use acrylic and methacrylic esters with alkyl groups consisting of 4 to 14 C atoms, more preferably 4 to 9 C atoms.
  • Examples of monomers of this kind are n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-amyl acrylate, n-hexyl acrylate, hexyl methacrylate, n-heptyl acrylate, n-octyl acrylate, n-octyl methacrylate, n-nonyl acrylate, isobutyl acrylate, isooctyl acrylate, isooctyl methacrylate, and their branched isomers, such as 2-ethylhexyl acrylate or 2-ethylhexyl methacrylate, for example.
  • the monomers of component (b) are, in particular, olefinically unsaturated monomers having functional groups, in particular having functional groups which are able to enter into a reaction with the epoxide groups.
  • Preference for component (b) is given to using monomers having functional groups which are selected from the group encompassing: hydroxyl, carboxyl, sulphonic acid or phosphonic acid groups, acid anhydrides, epoxides, amines.
  • monomers of component (b) are acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, dimethylacrylic acid, ⁇ -acryloyloxypropionic acid, trichloroacrylic acid, vinylacetic acid, vinylphosphonic acid, itaconic acid, maleic anhydride, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 6-hydroxyhexyl methacrylate, allyl alcohol, glycidyl acrylate, glycidyl methacrylate.
  • component (c) it is possible in principle to use all compounds with vinylic functionalization which are copolymerizable with component (a) and/or component (b).
  • the monomers of component (c) can serve to adjust the properties of the resultant PSA.
  • Monomers by way of example for component (c) are as follows:
  • Monomers of component (c) may advantageously also be selected such that they contain functional groups which support subsequent radiation-chemical crosslinking (by electron beams, UV, for example).
  • Suitable copolymerizable photoinitiators are, for example, benzoin acrylate and acrylate-functionalized benzophenone derivatives.
  • Monomers which support crosslinking by electron irradiation are, for example, tetrahydrofurfuryl acrylate, N-tert-butylacrylamide, and allyl acrylate.
  • the polyacrylates may be prepared by processes familiar to the skilled person, with particular advantage by conventional radical polymerizations or controlled free-radical polymerizations.
  • the polyacrylates may be prepared by copolymerization of the monomeric components using the usual polymerization initiators and also, where appropriate, regulators (chain transfer agents), with polymerization taking place at the customary temperatures in bulk, in emulsion, such as in water or liquid hydrocarbons, for example, or in solution.
  • the polyacrylates are prepared preferably by polymerization of the monomers in solvents, more particularly in solvents with a boiling range from 50 to 150° C., preferably from 60 to 120° C., using the customary amounts of polymerization initiators, these generally being 0.01% to 5%, more particularly 0.1% to 2%, by weight (based on the total weight of the monomers).
  • Suitable in principle are all customary initiators that are familiar to the skilled person.
  • free-radical sources are peroxides, hydroperoxides, and azo compounds, e.g., dibenzoyl peroxide, cumene hydroperoxide, cyclohexanone peroxide, di-tert-butyl peroxide, cyclohexylsulphonyl acetyl peroxide, diisopropyl percarbonate, tert-butyl peroctoate, benzopinacol.
  • Solvents contemplated include alcohols such as methanol, ethanol, n- and iso-propanol, n- and iso-butanol, preferably isopropanol and/or isobutanol; and also hydrocarbons such as toluene and, in particular, benzines with a boiling range from 60 to 120° C.
  • ketones such as, preferably, acetone, methyl ethyl ketone, methyl isobutyl ketone, and esters such as ethyl acetate, and also mixtures of solvents of the stated type, with preference going to mixtures containing isopropanol, particularly in amounts of 2% to 15% by weight, preferably 3% to 10% by weight, based on the solution mixture used.
  • the weight-average molecular weights M w of the polyacrylates are situated preferably within a range from 20 000 to 2 000 000 g/mol, very preferably within a range from 100 000 to 1 000 000 g/mol, and extremely preferably in a range from 150 000 to 500 000 g/mol;
  • the figures for the average molecular weight M w and for the polydispersity PD in this specification relate to the determination by gel permeation chromatography (see measurement method A2; Experimental Section).
  • suitable polymerization regulators such as thiols, halogen compounds and/or alcohols, in order to set the desired average molecular weight.
  • the polyacrylate preferably has a K value of 30 to 90, more preferably of 40 to 70, as measured in toluene (1% strength solution, 21° C.).
  • the K value according to Fikentscher is a measure of the molecular weight and viscosity of the polymer.
  • polyacrylates which have a narrow molecular weight distribution (polydispersity PD ⁇ 4).
  • polydispersity PD ⁇ 4 polydispersity
  • the lower molecular weight allows easier processing from the melt, since the flow viscosity is lower as compared with a broader-range polyacrylate, with largely the same application properties.
  • Narrow-range polyacrylates may be prepared, advantageously, by anionic polymerization or by controlled radical polymerization methods, the latter being especially suitable. Examples of polyacrylates of this kind which are prepared by the RAFT process are described in U.S. Pat. No. 6,765,078 B2 and U.S. Pat. No.
  • Polyacrylates of this kind can also be prepared via N-oxyls, as described in EP 1 311 555 B1, for example.
  • Atom Transfer Radical Polymerization (ATRP) as well can be employed advantageously for the synthesis of narrow-range polyacrylates, in which case it is preferred as initiator to use monofunctional or difunctional, secondary or tertiary halides and, for abstracting the halide(s), complexes of Cu, Ni, Fe, Pd, Pt, Ru, Os, Rh, Co, Ir, Ag or Au.
  • ATRP Atom Transfer Radical Polymerization
  • the polyacrylates to be crosslinked contain functional groups which are suitable for entering into linking reactions with epoxide groups.
  • linking reactions are meant, in particular, addition reactions and substitution reactions.
  • there is a linking of the units which carry the functional groups to the units which carry the epoxide groups more particularly in the sense of a crosslinking of the polymer units which carry the functional groups, via the epoxide-group-carrying crosslinker molecules as linking bridges.
  • the substances containing epoxide groups are preferably polyfunctional epoxides, in other words those having at least two epoxide groups; accordingly, there is overall an indirect linking of the units which carry the functional groups.
  • the crosslinkable composition of the invention may comprise at least one tackifying resin.
  • Tackifying resins which can be used are the existing tackifier resins described in the literature. Reference may be made in particular to all aliphatic, aromatic and alkylaromatic hydrocarbon resins, hydrocarbon resins based on pure monomers, hydrogenated hydrocarbon resins, functional hydrocarbon resins, and natural resins. With preference it is possible to use pinene resins and indene resins, and rosins, their disproportionated, hydrogenated, polymerized and esterified derivatives and salts, terpene resins and terpene-phenolic resins, and also C5 resins, C9 resins and other hydrocarbon resins.
  • the crosslinkable composition of the invention comprises terpene-phenolic resins and/or rosin esters.
  • the crosslinkable composition of the invention may optionally also comprise fillers in powder and/or granular form, likewise dyes and pigments, including more particularly abrasive and reinforcing fillers such as, for example, chalks (CaCO 3 ), titanium dioxides, zinc oxides and carbon blacks, even in high proportions, in other words from 1% to 50% by weight, based on the overall formula.
  • abrasive and reinforcing fillers such as, for example, chalks (CaCO 3 ), titanium dioxides, zinc oxides and carbon blacks, even in high proportions, in other words from 1% to 50% by weight, based on the overall formula.
  • chalks CaCO 3
  • titanium dioxides titanium dioxides
  • zinc oxides zinc oxides
  • carbon blacks even in high proportions, in other words from 1% to 50% by weight, based on the overall formula.
  • various forms of chalk as a filler, with particular preference being given to the use of Mikrosöhl chalk.
  • the addition of fillers produces virtually no change in
  • fillers of low flammability such as ammonium polyphosphate, for example; electrically conductive fillers such as conductive carbon black, carbon fibres and/or silver-coated beads, for example; thermally conductive materials such as boron nitride, aluminium oxide and silicon carbide, for example; ferromagnetic additives such as iron(III) oxides, for example; additives for increasing volume, more particularly for producing foamed layers or syntactic foams, such as, for example, expandants, solid glass beads, hollow glass beads, carbonized microbeads, hollow phenolic microbeads and microbeads of other materials, expandable microballoons (Expancel® from AkzoNobel), silica, silicates, organically renewable raw materials such as wood flour, for example, organic and/or inorganic nanoparticles, fibres; ageing inhibitors, light stabilizers, ozone inhibitors, compounding agents and/or expandants, may be present in the crosslinkable composition or in the fully
  • Ageing inhibitors which can be used are preferably not only primary inhibitors, such as 4-methoxyphenol or Irganox® 1076, but also secondary ageing inhibitors, such as Irgafos® TNPP or Irgafos® 168 from BASF, optionally also in combination with one another.
  • Other ageing inhibitors which can be used are phenothiazine (C radical scavenger) and also hydroquinone methyl ether in the presence of oxygen, and also oxygen itself.
  • Plasticizers which can be metered in are, for example, low molecular weight polyacrylates, phthalates, water-soluble plasticizers, plasticizer resins, phosphates, polyphosphates, adipates and/or citrates.
  • the thermally crosslinkable and/or crosslinked polyacrylate or polyacrylates may in accordance with the invention also be blended with other polymers.
  • Suitable for this purpose are polymers based on natural rubber, synthetic rubber, EVA, silicone rubber, acrylic rubber and polyvinyl ether. It has proven to be useful to add these polymers in granulated or otherwise comminuted form to the polyacrylate before the thermal crosslinker is added.
  • the polymer blends are produced preferably in an extruder, more preferably in a multi-screw extruder or in a planetary roller extruder.
  • thermally crosslinked polyacrylates especially polymer blends of thermally crosslinked acrylate hotmelts and other polymers
  • crosslinking promoters such as di-, tri- or polyfunctional acrylate, polyesters and/or urethane acrylate.
  • a further subject of the invention is a crosslinked polyacrylate which is obtainable by thermal crosslinking of the crosslinkable composition of the invention.
  • a further subject of the invention is a process for the thermal crosslinking of polyacrylates having functional groups which are suitable for entering into linking reactions with epoxide groups, said process encompassing the use of a crosslinker-accelerator system of the invention.
  • the process of the invention may include a concentration of the polyacrylate solution or dispersion resulting from the polymer preparation procedure. Concentration of the polymer may take place in the absence of the crosslinker and accelerator substances. It is also possible, however, for one at most of these substances to be added to the polymer even before concentration, in which case the concentration takes place in the presence of this or these substance(s).
  • the polymerisates are then preferably transferred to a compounder.
  • concentration and compounding may take place in the same reactor.
  • the compounder used may in particular be an extruder.
  • the polymerisates are present preferably in the melt, either because they are in the melt state when they are introduced, or by virtue of their heating in the compounder until a melt is formed.
  • the polymerisates are advantageously held in the melt in the compounder by heating.
  • the possible temperature in the melt is limited by the decomposition temperature of the polymerisate.
  • the operational temperature within the compounder is typically between 80 to 150° C., more particularly between 100 and 120° C.
  • the substances containing epoxide groups are added to the polymer preferably before or with the addition of accelerator. They may be added to the monomers even before or during the polymerization phase, if they are sufficiently stable for that phase. With particular preference, however, the substances containing epoxide groups are added to the polymerisate either before addition to the compounder or during addition to the compounder, in other words are introduced into the compounder together with the polymerisates.
  • the accelerator substances are added to the polymerisates shortly before further processing, more particularly before a coating or other shaping operation.
  • the time window for the addition prior to coating is guided in particular by the potlife which is available, in other words the processing life in the melt, without deleterious change to the properties of the resultant product.
  • the accelerator is advantageously added as late as possible to the melt, but as early as necessary, so that there is still effective homogenization with the polymer composition.
  • Time periods which have emerged as being very advantageous here are those from 2 to 10 minutes, more particularly those of more than 5 minutes, before the beginning of further processing, at an operating temperature of 110 to 120° C.
  • crosslinkers (epoxides) and the accelerators can also both be added shortly before the further processing of the polymer, in other words advantageously in the phase as set out above for the accelerators.
  • crosslinkers and accelerators are introduced into the operation simultaneously, at the same location, possibly in the form of an epoxide-accelerator blend.
  • the temperature of the polymerisate on addition of the crosslinkers and/or accelerators is preferably between 50 and 150° C., more preferably between 70 and 130° C. and very preferably between 80 and 120° C.
  • the crosslinker i.e. the substance containing epoxide groups
  • the accelerator at 0.1%-5% by weight, more preferably at 0.1%-1.2% by weight, based on the additive-free polymer.
  • the crosslinker fraction is selected so as to result in an elastic fraction of the crosslinked polyacrylates of at least 20%.
  • the elastic fraction is preferably at least 40%, more preferably at least 60% (measured in each case by measurement method H3; cf. Experimental Section).
  • the polymer composition cools relatively rapidly, down to the storage temperature, generally to room temperature.
  • the crosslinker-accelerator system of the invention is outstandingly suitable for causing the crosslinking reaction to progress without the supply of further thermal energy (without heat supply).
  • the inventive accelerator or accelerators and accelerator concentrations may advantageously be selected such that the elastic fraction of the polyacrylate after departure from the compounding operation, at lower temperatures than in the operation, such as at room temperature, for example, exceeds a level of 25%, preferably of 35%, within a week, preferably within three days, so that there is already a functional product (more particularly an adhesive tape or a functional carrier layer based on the polyacrylate).
  • crosslinking reaction between the functional groups of the polyacrylate and the epoxides by means of the crosslinker-accelerator system of the invention, thus proceeds even without supply of heat under standard conditions, more particularly at room temperature, to completion.
  • the proportions of the constituents of the crosslinker-accelerator system of the invention to one another or to the polyacrylate to be crosslinked it is possible to use the ratio of the number of epoxide groups in the crosslinker to the number of reactive functional groups in the polyacrylate. In principle this ratio can be selected freely, with either an excess of functional groups, numerical equality of the groups, or an excess of epoxide groups.
  • This ratio is preferably selected such that the epoxide groups are in deficit or at most in numerical equality; with very particular preference, the ratio of the total number of epoxide groups in the crosslinker to the number of functional groups in the polyacrylate that are suitable for entering into linking reactions with epoxide groups is in the range from 0.01:1 to 1:1, more particularly in the range from 0.02:1 to 0.4:1.
  • the functional groups, more preferably carboxylic acid groups, in the polyacrylate are present in an excess over the epoxide groups, so that the polymerisate contains a sufficiently large number of functional groups—that is, potential crosslinking or linking sites—in order to achieve the desired crosslinking.
  • the ratio of the number of acceleration-active groups in the accelerator to the number of epoxide groups in the crosslinker may in principle be selected freely, so there is alternatively an excess of acceleration-active groups, numerical equality of the groups, or an excess of epoxide groups.
  • Groups considered to be acceleration-active groups are amino groups and phosphino groups, terms which comprehend all primary, secondary and tertiary, and hence all substituted and unsubstituted, amino and phosphino groups.
  • the ratio of the number of all the substituted and unsubstituted amino and phosphino groups in the accelerator to the number of epoxide groups in the crosslinker is preferably from 0.2:1 to 4:1.
  • the polymer can be processed further, more particularly by coating onto a permanent or temporary carrier.
  • a permanent carrier remains joined to the layer of adhesive in the application, whereas the temporary carrier is removed in the course of further processing, as for example when converting the adhesive tape, or at the time of application of the layer of adhesive.
  • Coating of the self-adhesive compositions may take place using hotmelt coating nozzles known to the skilled person, or, preferably, using roll applicator mechanisms, also called coating calenders.
  • the coating calenders may consist advantageously of two, three, four or more rolls.
  • At least one of the rolls is provided with an anti-adhesive roll surface, this being true preferably of all of the rolls that come into contact with the polyacrylate.
  • An anti-adhesive roll surface used is preferably a steel-ceramic-silicone composite. Roll surfaces of this kind are resistant to thermal and mechanical loads.
  • roll surfaces are used that have a surface structure, more particularly of a kind such that the surface does not produce full contact with the polymer layer to be processed, but instead such that the area of contact is lower as compared with a smooth roll.
  • Particularly advantageous are structured rolls such as engraved metal rolls—engraved steel rolls, for example.
  • Coating may take place with particular advantage in accordance with the coating techniques set out in WO 2006/027387 A1 from page 12, line 5 to page 20, line 13, and more particularly as in the sections “Variant A” (page 12), “Variant B” (page 13), “Variant C” (page 15), “Method D” (page 17), “Variant E” (page 19) and also FIGS. 1 to 6 .
  • the stated disclosure passages from WO 2006/027387 A1 are therefore explicitly included in the disclosure content of the present specification.
  • FIG. 1 shows a compounding and coating operation in a continuous process.
  • FIG. 2 is a graph depicting the effect of epoxide concentration on the degree of crosslinking for a given amount of accelerator and a given temperature.
  • FIG. 3 is a graph depicting the effect of accelerator concentration for a given temperature (in this case room temperature) and with a constant amount of epoxide.
  • FIG. 4 shows a process for making a three-layer composition by 2-roll calendar.
  • FIG. 5 is a graph depicting the complex viscosities of different polymer-accelerator mixtures with the same number of basic amino groups.
  • FIG. 1 of the present specification Shown by way of example in FIG. 1 of the present specification is the compounding and coating operation, on the basis of a continuous process.
  • the polymers are introduced at the first feed point ( 1 . 1 ) into the compounder ( 1 . 3 ), here for example an extruder. Either the introduction takes place already in the melt, or the polymers are heated in the compounder until the melt state is reached.
  • the epoxide-containing compounds are advantageously introduced into the compounder.
  • the accelerators are added at a second feed point ( 1 . 2 ).
  • the outcome of this is that the accelerators are added to the epoxide-containing polymers not until shortly before coating, and the reaction time in the melt is low.
  • the reaction regime may also be discontinuous.
  • the addition of the polymers, of the crosslinkers and of the accelerators may take place at different times and not, as shown in FIG. 1 , at different locations.
  • the polymer Immediately after coating—preferably by means of roll application or by means of an extrusion die—the polymer is only slightly crosslinked, but not yet sufficiently crosslinked.
  • the crosslinking reaction preferably proceeds predominantly on the carrier.
  • Crosslinking raises the cohesion of the polymer and hence also the shear strength.
  • the links are very stable. This allows very ageing-stable and heat-resistant products to be produced, such as adhesive tapes, viscoelastic carrier materials or shaped articles.
  • the physical properties of the end product can be influenced through the degree of crosslinking, and so the end product can be optimized through an appropriate choice of the reaction conditions.
  • a variety of factors determine the operational window of this process.
  • the most important influencing variables are the amounts (concentrations and proportions relative to one another), the chemical nature of the crosslinkers and the accelerators, the operating and coating temperatures, the residence time in the compounder (more particularly extruder) and in the coating assembly, the fraction of functional groups, more particularly acid groups and/or hydroxyl groups, in the polymer, and also the average molecular weight of the polyacrylate.
  • the crosslinker-accelerator system of the invention offers the advantage that a stable crosslinking process for polyacrylates can be offered, and one with outstanding control facility in relation to the crosslinking pattern, by virtue of substantial decoupling of degree of crosslinking and reactivity (reaction kinetics), more particularly the reaction kinetics at low temperatures.
  • the amount of crosslinker (amount of epoxide) added here largely influences the degree of crosslinking of the product, and the chemical nature and concentration of the accelerator largely control the reactivity.
  • the effect of epoxide group concentration on the degree of crosslinking for a given amount of accelerator and a given temperature is shown schematically by FIG. 2 .
  • the accelerator concentration rises from the concentration A (top curve; low concentration) via the concentrations B (second-lowest concentration) and C (second-highest concentration) to the concentration D (bottom curve; highest concentration).
  • the final value of the degree of crosslinking represented here by increasingly smaller values for the microshear travel—goes up as the epoxide concentration increases, whereas the reaction kinetics remain virtually unaffected.
  • the amount of accelerator added has a direct influence on the crosslinking rate, and hence also on the point in time at which the final degree of crosslinking is achieved, but without influencing it absolutely.
  • the reactivity of the crosslinking reaction here may be selected such that the crosslinking also during storage of the completed product under the conditions customary therein (room temperature) leads within a few weeks to the desired degree of crosslinking, more particularly without any need for thermal energy to be (actively) supplied or for the product to be treated further.
  • the reactivity of the crosslinking reaction can also be influenced by varying the temperature, if desired, especially in those cases where the advantage of “inherent crosslinking” in the course of storage under standard conditions has no part to play.
  • a constant crosslinker concentration an increase in the operating temperature leads to a reduced viscosity, which enhances the coatability of the composition but reduces the processing life.
  • An increase in the processing life is acquired by a reduction in the accelerator concentration, reduction in molecular weight, reduction in the concentration of functional groups in the addition polymer, reduction of the acid fraction in the addition polymer, use of less-reactive crosslinkers (epoxides) or of less-reactive crosslinker-accelerator systems, and reduction in operating temperature.
  • an improvement in the cohesion of the composition can be obtained by a variety of pathways.
  • the accelerator concentration is increased, which reduces the processing life.
  • it also possible to raise the molecular weight of the polyacrylate, which is possibly more efficient.
  • it is advantageous in any case to raise the concentration of crosslinker (substances containing epoxide groups).
  • crosslinker substances containing epoxide groups
  • a further subject of the invention is the use of a crosslinker-accelerator system of the invention for producing thermally crosslinked polyacrylates.
  • Inventively crosslinked polyacrylates can be used for a broad range of applications. Below, a number of particularly advantageous fields of use are set out by way of example.
  • a polyacrylate crosslinked with the crosslinker-accelerator system of the invention is used in particular as a pressure-sensitive adhesive (PSA), preferably as a PSA for an adhesive tape, where the acrylate PSA is in the form of a single-sided or double-sided film on a carrier sheet.
  • PSA pressure-sensitive adhesive
  • These polyacrylates are especially suitable when a high coat weight in one coat is required, since with this coating technique it is possible to achieve an almost arbitrarily high coat weight, preferably more than 100 g/m 2 , more preferably more than 200 g/m 2 , and to do so in particular at the same time as homogeneous crosslinking through the coat.
  • Examples of favourable applications are technical adhesive tapes, more especially for use in construction, examples being insulating tapes, corrosion control tapes, adhesive aluminium tapes, fabric-reinforced film-backed adhesive tapes (duct tapes), special-purpose adhesive construction tapes, such as vapour barriers, adhesive assembly tapes, cable wrapping tapes, self-adhesive sheets and/or paper labels.
  • the inventively crosslinked polyacrylate may also be made available as a PSA for a carrierless adhesive tape, in the form of what is called an adhesive transfer tape.
  • a carrierless adhesive tape in the form of what is called an adhesive transfer tape.
  • Preferred weights per unit area are more than 10 g/m 2 to 5000 g/m 2 , more preferably 100 g/m 2 to 3000 g/m 2 .
  • inventively crosslinked polyacrylate may also be present in the form of a heat-sealing adhesive in adhesive transfer tapes or single-sided or double-sided adhesive tapes.
  • the carrier may be an inventively obtained viscoelastic polyacrylate.
  • One advantageous embodiment of the adhesive tapes obtained using an inventively crosslinked polyacrylate can be used as a strippable adhesive tape, more particularly a tape which can be detached again without residue by pulling substantially in the plane of the bond.
  • crosslinker-accelerator system of the invention or the crosslinker composition of the invention is also particularly suitable for producing three-dimensional shaped articles, whether they be tacky or not.
  • a particular advantage of this process is that there is no restriction on the layer thickness of the polyacrylate to be crosslinked and shaped, in contrast to UV and EBC curing processes. In accordance with the choice of coating assembly or shaping assembly, therefore, it is possible to produce structures of any desired shape, which are then able to continue crosslinking to desired strength under mild conditions.
  • This system or composition is also particularly suitable for the production of particularly thick layers, especially of pressure-sensitive adhesive layers or viscoelastic acrylate layers, with a thickness of more than 80 ⁇ m.
  • Layers of this kind are difficult to produce with the solvent technology, since, for example, this technology entails bubble formation and very slow coating speeds.
  • the alternative lamination of thin layers one over another is complicated and harbours weak points.
  • Thick pressure-sensitive adhesive layers may be present, for example, in unfilled form, as straight acrylate, or in resin-blended form or in a form filled with organic or inorganic fillers. Also possible is the production of layers foamed to a closed-cell or open-cell form in accordance with the known techniques, as well as of syntactic foams, using the crosslinker-accelerator system of the invention or the thermally crosslinkable composition of the invention. Possible methods of foaming are those of foaming via compressed gases such as nitrogen or CO 2 , or foaming via expandants such as hydrazines or expandable microballoons. Where expandable microballoons are used, the composition or the shaped layer is advantageously activated suitably by means of heat introduction.
  • Foaming may take place in the extruder or after coating. It may be judicious to smooth the foamed layer by means of suitable rollers or release films. To produce foam-analogous layers it is also possible to add hollow glass beads or pre-expanded polymeric microballoons to the tacky, thermally crosslinked polyacrylate.
  • thick layers as well which can be used as a carrier layer for double-sidedly PSA-coated adhesive tapes.
  • these are filled and foamed layers which can be utilized as carrier layers for foamlike adhesive tapes.
  • hollow glass beads, solid glass beads or expanding microballoons to the polyacrylate prior to the addition of the crosslinker-accelerator system or of the crosslinker or of the accelerator.
  • a pressure-sensitive adhesive layer onto at least one side of a foamlike viscoelastic layer of this kind. It is preferred to laminate a corona-pretreated polyacrylate layer on both sides.
  • Suitable base polymers are adhesives based on natural rubber, synthetic rubbers, acrylate block copolymers, styrene block copolymers, EVA, certain polyolefins, specific polyurethanes, polyvinyl ethers, and silicones.
  • Preferred compositions are those which have no significant fraction of migratable constituents and whose compatibility with the polyacrylate is so good that they diffuse in significant quantities into the acrylate layer and alter the properties therein.
  • Asymmetric adhesive tapes of this kind allow the bonding of critical substrates with a high bonding strength.
  • An adhesive tape of this kind can be used, for example, to affix EPDM rubber profiles to vehicles.
  • inventively crosslinked polyacrylates are that these layers, whether utilized as a viscoelastic carrier, as a pressure-sensitive adhesive or as a heat-sealing composition, combine an equal surface quality with no crosslinking profile through the layer (or, correspondingly, through the shaped article produced from the polyacrylates)—in particular in contrast to UV-crosslinked and EBC-crosslinked layers.
  • the balance between adhesive and cohesive properties it is possible for the balance between adhesive and cohesive properties to be controlled and set ideally for the layer as a whole through the crosslinking.
  • radiation-crosslinked layers in contrast, there is generally one side or one sublayer which is over- or undercrosslinked.
  • the K value is a measure of the average molecular size of high-polymer materials. It is measured by preparing one percent strength (1 g/100 ml) toluenic polymer solutions and determining their kinematic viscosities using a Vogel-Ossag viscometer. Standardization to the viscosity of the toluene gives the relative viscosity, from which the K value can be calculated by the method of Fikentscher ( Polymer 1967, 8, 381ff.)
  • the figures for the weight-average molecular weight M w and the polydispersity PD in this specification relate to the determination by gel permeation chromatography. Determination is made on a 100 ⁇ l sample subjected to clarifying filtration (sample concentration 4 g/l). The eluent used is tetrahydrofuran with 0.1% by volume of trifluoroacetic acid. Measurement takes place at 25° C. The preliminary column used is a column type PSS-SDV, 5 ⁇ , 10 3 ⁇ , ID 8.0 mm 50 mm.
  • Separation is carried out using the columns of type PSS-SDV, 5 ⁇ , 10 3 ⁇ and also 10 5 ⁇ and 10 6 ⁇ each with ID 8.0 mm ⁇ 300 mm (columns from Polymer Standards Service; detection by means of Shodex RI71 differential refractometer). The flow rate is 1.0 ml per minute. Calibration takes place against PMMA standards (polymethyl methacrylate calibration).
  • the solids content is a measure of the fraction of non-evaporable constituents in a polymer solution. It is determined gravimetrically, by weighing the solution, then evaporating the evaporable fractions in a drying cabinet at 120° C. for 2 hours and reweighing the residue.
  • the measurement requires a bubble-free specimen with a layer thickness of at least 1 mm and an edge length of approximately 1 cm.
  • the specimen can be obtained, for example, by hot pressing of bubbly polymer composition or by bubble-free lamination of two or more plies of a swatch specimen one above another. The specimen is subsequently placed onto the sample plate of the rheometer, and the top plate is pressed onto the specimen under a defined force.
  • Instrument DSR I or DSR II, measuring head 200 g air-mounted with standard force, thermal conditioning: Peltier element, measuring geometry: parallel plates, diameter: 25.0 mm
  • Measurement frequency 10 rad/s, temperature range: ⁇ 40° C. to 130° C., heating rate: 2.5° C./min, stress: 2500 Pa.
  • a strip 20 mm wide of an acrylate PSA applied to polyester as a layer was applied to steel plates which beforehand had been washed twice with acetone and once with isopropanol.
  • the pressure-sensitive adhesive strip was pressed onto the substrate twice with an applied pressure corresponding to a weight of 2 kg.
  • the adhesive tape was then removed from the substrate immediately with a speed of 300 mm/min and at an angle of 180°. All measurements were conducted at room temperature.
  • a strip of the adhesive tape 13 mm wide and more than 20 mm long (30 mm, for example) was applied to a smooth steel surface which had been cleaned three times with acetone and once with isopropanol.
  • the bond area was 20 mm ⁇ 13 mm (length ⁇ width), the adhesive tape protruding beyond the test plate at the edge (by 10 mm, for example, corresponding to aforementioned length of 30 mm).
  • the adhesive tape was pressed onto the steel support four times, with an applied pressure corresponding to a weight of 2 kg. This sample was suspended vertically, with the protruding end of the adhesive tape pointing downwards.
  • the holding power times measured are reported in minutes and correspond to the average value from three measurements.
  • This test serves for the accelerated testing of the shear strength of adhesive tapes under temperature load.
  • An adhesive tape (length about 50 mm, width 10 mm) cut from the respective sample specimen is adhered to a steel test plate, which has been cleaned with acetone, in such a way that the steel plate protrudes beyond the adhesive tape to the right and the left, and that the adhesive tape protrudes beyond the test plate by 2 mm at the top edge.
  • the bond site is subsequently rolled over six times with a 2 kg steel roller at a speed of 10 m/min.
  • the adhesive tape is reinforced flush with a stable adhesive strip which serves as a support for the travel sensor.
  • the sample is suspended vertically by means of the test plate.
  • the sample specimen for measurement is loaded at the bottom end with a weight of 100 g.
  • the test temperature is 40° C., the test duration 30 minutes (15 minutes' loading and 15 minutes' unloading).
  • the shear travel after the predetermined test duration at constant temperature is reported as the result in ⁇ m, as both the maximum value [“max”; maximum shear travel as a result of 15-minute loading]; and the minimum value [“min”; shear travel (“residual deflection”) 15 minutes after unloading; on unloading there is a backward movement as a result of relaxation].
  • the bond strength to steel is determined under test conditions of 23° C.+/ ⁇ 1° C. temperature and 50%+/ ⁇ 5% relative humidity.
  • the specimens were cut to a width of 20 mm and adhered to a steel plate.
  • the steel plate Prior to the measurement the steel plate is cleaned and conditioned. For this purpose the plate is first wiped down with acetone and then left to stand in the air for 5 minutes to allow the solvent to evaporate.
  • the side of the three-layer assembly facing away from the test substrate was then lined with a 50 ⁇ m aluminium foil, thereby preventing the sample from expanding in the course of the measurement. This was followed by the rolling of the test specimen onto the steel substrate.
  • the tape was rolled over 5 times back and forth, with a rolling speed of 10 m/min, using a 2 kg roller.
  • the steel plate was inserted into a special mount which allows the specimen to be removed at an angle of 90° vertically upwards.
  • the measurement of bond strength was made using a Zwick tensile testing machine.
  • Specimen preparation took place under test conditions of 23° C.+/ ⁇ 1° C. temperature and 50%+/ ⁇ 5% relative humidity.
  • the test specimen was cut to 13 mm and adhered to a steel plate.
  • the bond area is 20 mm ⁇ 13 mm (length ⁇ width).
  • the steel plate was cleaned and conditioned. For this purpose the plate was first wiped down with acetone and then left to stand in the air for 5 minutes to allow the solvent to evaporate. After bonding had taken place, the open side was reinforced with a 50 ⁇ m aluminium foil and rolled over back and forth 2 times using a 2 kg roller. Subsequently a belt loop was attached to the protruding end of the three-layer assembly.
  • the whole system was then suspended from a suitable device and subjected to a load of 10 N.
  • the suspension device is such that the weight loads the sample at an angle of 179°+/ ⁇ 1°. This ensures that the three-layer assembly is unable to peel from the bottom edge of the plate.
  • the measured holding power, the time between suspension and dropping of the sample is reported in minutes and corresponds to the average value from three measurements.
  • To measure the lined side the open side is first reinforced with the 50 ⁇ m aluminium foil, the release material is removed, and adhesion to the test plate takes place as described. The measurement is conducted under standard conditions (23° C., 55% humidity).
  • the polymers investigated are prepared conventionally via free radical polymerization in solution.
  • a reactor conventional for free-radical polymerizations was charged with 30 kg of 2-ethylhexyl acrylate, 67 kg of n-butyl acrylate, 3 kg of acrylic acid, and 66 kg of acetone/isopropanol (96:4). After nitrogen gas had been passed through the reactor for 45 minutes with stirring, the reactor was heated to 58° C. and 50 g of 2,2′-azobis(2-methylbutyronitrile) were added. Subsequently the external heating bath was heated to 75° C. and the reaction was carried out constantly at this external temperature. After 1 h a further 50 g of 2,2′-azobis(2-methylbutyronitrile) were added, and after 4 h the batch was diluted with 20 kg of acetone/isopropanol mixture (96:4).
  • the acrylate copolymers (base polymers P1 and P2) are very largely freed from the solvent by means of a single-screw extruder (concentrating extruder, Berstorff GmbH, Germany) (residual solvent content ⁇ 0.3% by weight; cf. the individual examples).
  • the parameters given here by way of example are those for the concentration of base polymer P1.
  • the screw speed was 150 rpm, the motor current 15 A, and a throughput of 58.0 kg liquid/h was realized.
  • a vacuum was applied at 3 different domes.
  • the reduced pressures were, respectively, between 20 mbar and 300 mbar.
  • the exit temperature of the concentrated hotmelt is approximately 115° C.
  • the solids content after this concentration step was 99.8%.
  • the resin Dertophene® T105 was metered in zone 1 and mixed in homogeneously.
  • no resin was metered in; instead, the hollow thermoplastic microbeads, mixed to a paste with Levagard® DMPP beforehand, were metered in via the solids metering system.
  • the parameters given here by way of example are those for resin compounding with base polymer P1. Speed was 451 rpm, the motor current 42 A, and a throughput of 30.1 kg/h was realized.
  • the temperatures of zones 1 and 2 were each 105° C., the melt temperature in zone 1 was 117° C., and the composition temperature on exit (zone 3) was 100° C.
  • the acrylate hotmelt PSAs prepared by Processes 1-2 were melted in a feeder extruder (single-screw conveying extruder from Troester GmbH & Co. KG, Germany) and using this extruder were conveyed as a polymer melt into a twin-screw extruder (Leistritz, Germany, ref. LSM 30/34).
  • the assembly is heated electrically from the outside and is air-cooled by a number of fans, and is designed such that, with effective distribution of the crosslinker-accelerator system in the polymer matrix, there is at the same time a short residence time ensured for the adhesive in the extruder.
  • the mixing shafts of the twin-screw extruder were arranged in such a way that conveying elements are in alternation with mixing elements.
  • the addition of the respective crosslinkers and accelerators is made with suitable metering equipment, where appropriate at two or more points ( FIG. 1 : metering points 1 . 1 and 1 . 2 ) and, where appropriate, with the use of metering assistants into the unpressurized conveying zones of the twin-screw extruder.
  • the ready-compounded adhesive i.e. of the adhesive blended with the crosslinker-accelerator system
  • coating takes place in accordance with FIG. 1 onto a carrier material in web form.
  • the processing life indicates the period within which the adhesive, blended with the crosslinker-accelerator system, or the viscoelastic carrier layer, can be coated with a visually good appearance (gel-free, speck-free). Coating takes place with web speeds between 1 m/min and 20 m/min; the doctor roll of the 2-roll applicator is not driven.
  • the base polymer P3 was blended with 0.2% by weight of Uvacure® 1500, based on the polymer, then diluted with acetone to a solids content of 30% (measurement method A3) and subsequently coated from solution onto a siliconized release film (50 ⁇ m polyester) and onto a 23 ⁇ m etched PET film (coating speed of 2.5 m/min, drying tunnel 15 m, temperatures: Zone 1: 40° C., Zone 2: 70° C., Zone 3: 95° C., Zone 4: 105° C.).
  • the coat weight was 50 g/m 2 .
  • the base polymer P1 was polymerized in accordance with the polymerization process described, concentrated in accordance with Process 1 (solids content 99.8%) and then blended with Dertophene® T105 resin in accordance with Process 2. This resin-modified acrylate hotmelt composition was then compounded in accordance with Process 3 continuously with the crosslinker-accelerator system (see Table 1).
  • the crosslinker system used was diluted with the liquid dimethyl propylphosphonate Levagard® DMPP from Lanxess (ratio of the crosslinker 0.5:1). Since the operation was carried out in the same way in each case, the operational parameters are no longer explicitly recited.
  • the processing life of the completed compounded formulations was more than 7 minutes with an average composition temperature of 125° C. after departure from the Leistritz twin-screw extruder. Coating takes place on a 2-roll applicator in accordance with FIG. 1 , at roll surface temperatures of 100° C. in each case and with a coat weight each of 100 g/m 2 onto 23 ⁇ m PET film.
  • On the adhesive tapes thus produced measurements were made of the bond strength to steel at room temperature and microshear travel at 40° C. as a function of the storage time. After 14 days of room-temperature storage, the maximum microshear travel is not significantly different.
  • Table 4 The technical adhesive data of Examples B1 to B5 are summarized in Table 4. These examples show that very high-performance adhesive tapes can be produced, featuring, among other qualities, high bond strengths to polar and apolar substrates (steel and polyethylene) and good cohesive properties even under the influence of temperature.
  • the examples were carried out in each case with the polymer P1, with the epoxide crosslinker pentaerythritol tetraglycidyl ether (Polypox® R 16 from UPPC, 0.19% by weight based on polymer) and with the resin Dertophene® T105 (from DRT, 32% by weight based on polymer).
  • the amount of accelerator was selected such that the number of activating basic groups is constant (see Table 2). Because of the different number of functionalities per molecule, there is therefore variation in the amount-of-substance concentration, based on the molecule. Where amino alcohols are used as accelerators, there is in each case only one hydroxyl group present per molecule; the comparative examples relate to amine accelerators with the same number of activating basic amine functionalities.
  • the crosslinking reaction proceeds to completion via the functional groups of the polyacrylate, even without supply of heat, under standard conditions (room temperature).
  • room temperature under standard conditions
  • the crosslinking reaction has concluded to an extent such that an adhesive tape or carrier layer present is functional.
  • the ultimate crosslinking state and hence the ultimate cohesion of the composition are achieved, depending on the choice of the composition/crosslinker system, after a storage time of 14 to 30 days, in advantageous form after 14 to 21 days' storage time at room temperature, expected to be earlier in the case of a higher storage temperature.
  • the base polymer P1 was polymerized in accordance with the polymerization process described, concentrated in accordance with Process 1 (solids content 99.8%) and then blended with Dertophene® T105 resin in accordance with Process 2. This resin-modified acrylate hotmelt composition was then compounded in accordance with Process 3 continuously with the crosslinker-accelerator system.
  • the crosslinker system used was diluted with the liquid dimethyl propylphosphonate Levagard® DMPP from Lanxess (ratio of the crosslinker 0.5:1). Since the operation was carried out in each case in the same way, analogously to Example B1, the operational parameters are no longer explicitly recited.
  • the processing life of the completed compounded formulations was more than 7 minutes with an average composition temperature of 125° C. after departure from the Leistritz twin-screw extruder. Coating takes place on a 2-roll applicator in accordance with FIG. 1 , at roll surface temperatures of 100° C. in each case and with a coat weight each of 100 g/m 2 onto 23 ⁇ m PET film. On the adhesive tapes thus produced, measurements were made of the bond strength to steel at room temperature and microshear travel at 40° C. as a function of the storage time. After 14 days of room-temperature storage, the maximum microshear travel is not significantly different.
  • Table 4 The technical adhesive data of Examples B6 to B8 are summarized in Table 4.
  • the base polymer P2 was freed in the same way as in Process 1 from the solvents, and then optionally was admixed with additives in the same way as in Process 2. Thereafter the process was carried out as described in FIG. 4 .
  • the viscoelastic composition ( 3 ) already compounded with the crosslinker-accelerator system and with fillers where appropriate, is supplied to the roll nip.
  • the shaping of the viscoelastic composition to a viscoelastic film takes place between the calender rolls (W 1 ) and (W 2 ) in the roll nip between two self-adhesive compositions ( 6 a , 6 b ), which in turn are supplied in a form where they are coated on anti-adhesively furnished carrier materials ( 5 a , 5 b ).
  • the viscoelastic composition is shaped to the set layer thickness, and is coated with the two self-adhesive compositions supplied.
  • the self-adhesive compositions are corona-treated by corona station ( 8 ) (corona unit from Vitaphone, Denmark, 100 W ⁇ min/m 2 ) before being supplied to the roll nip. After the three-layer assembly has been produced, this treatment leads to improved chemical attachment to the viscoelastic carrier layer.
  • the web speed when travelling through the coating unit is 30 m/min.
  • any anti-adhesive carrier ( 5 a ) is removed, and the completed three-layer product ( 9 ) is wound up with the remaining, second anti-adhesive carrier ( 5 b ).
  • the base polymer P2 was concentrated by Process 1 (solids content 99.7%) and then compounded by Process 3 in a twin-screw extruder continuously with
  • MT1 the crosslinker-accelerator system consisting of
  • the double-sided adhesive assembly tapes of the invention have very good technical adhesive data. Particularly positive is the balanced adhesive profile of the respective sides. With the same layer of adhesive on both sides of the adhesive tape, these sides exhibit virtually the same technical adhesive data. This shows the homogeneous crosslinking through the layer. Moreover, these three-layer adhesive tapes do not exhibit any delamination. By virtue of the corona treatment of the pressure-sensitive adhesive layers and the secondary crosslinking of the adjacent viscoelastic carrier layer, the anchoring of the layers to one another is very good.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US13/745,298 2012-01-20 2013-01-18 Crosslinker-accelerator system for polyacrylates Active 2034-03-14 US10174139B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102012200855.1 2012-01-20
DE102012200855A DE102012200855A1 (de) 2012-01-20 2012-01-20 Vernetzer-Beschleuniger-System für Polyacrylate
DE102012200855 2012-01-20

Publications (2)

Publication Number Publication Date
US20130190460A1 US20130190460A1 (en) 2013-07-25
US10174139B2 true US10174139B2 (en) 2019-01-08

Family

ID=48742370

Family Applications (1)

Application Number Title Priority Date Filing Date
US13/745,298 Active 2034-03-14 US10174139B2 (en) 2012-01-20 2013-01-18 Crosslinker-accelerator system for polyacrylates

Country Status (4)

Country Link
US (1) US10174139B2 (ja)
JP (1) JP2013147654A (ja)
CN (1) CN103214773B (ja)
DE (1) DE102012200855A1 (ja)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012200853A1 (de) * 2012-01-20 2013-07-25 Tesa Se Vernetzer-Beschleuniger-System für Polyacrylate
EP3034576B1 (en) 2014-12-18 2019-06-26 3M Innovative Properties Company Pressure sensitive adhesive for outdoor applications
EP3034575A1 (en) 2014-12-18 2016-06-22 3M Innovative Properties Company Pressure sensitive adhesive for outdoor applications
EP3159386B1 (en) 2015-10-23 2021-08-25 3M Innovative Properties Company Thermally post-curable pressure sensitive adhesive
DE102016221843A1 (de) * 2016-11-08 2018-05-09 Tesa Se Klebesystem aus mehreren Haftklebmasseschichten
DE102017221039B4 (de) * 2017-11-24 2020-09-03 Tesa Se Verfahren zur Herstellung einer Haftklebemasse auf Basis von Acrylnitril-Butadien-Kautschuk
EP3587528B1 (en) 2018-06-22 2021-05-26 3M Innovative Properties Company Process of manufacturing a pressure sensitive adhesive having low voc characteristics
EP3587529B1 (en) 2018-06-22 2022-07-27 3M Innovative Properties Company Hot melt process for manufacturing a pressure sensitive adhesive having low voc characteristics
CN111334196B (zh) * 2020-03-20 2022-02-18 山东非金属材料研究所 一种复合材料发动机壳体界面粘接用胶及其制备方法

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4051195A (en) 1975-12-15 1977-09-27 Celanese Polymer Specialties Company Polyepoxide-polyacrylate ester compositions
US4524104A (en) 1981-08-25 1985-06-18 Sanyo Chemical Industries, Ltd. Adhesive composition and laminates therefrom
EP0752435A2 (de) 1995-07-04 1997-01-08 Beiersdorf Aktiengesellschaft Vernetzung von Acrylat-Schmelzhaftklebern
US5789487A (en) 1996-07-10 1998-08-04 Carnegie-Mellon University Preparation of novel homo- and copolymers using atom transfer radical polymerization
US5854364A (en) 1996-12-26 1998-12-29 Elf Atochem S.A. Process for the controlled radical polymerization or copolymerization of (meth)acrylic, vinyl, vinylidene and diene monomers, and (co)polymers obtained
US6720399B2 (en) 2001-10-05 2004-04-13 Tesa Ag UV-crosslinkable acrylic hotmelt PSAs with narrow molecular weight distribution
US20040092685A1 (en) 2000-07-28 2004-05-13 Marc Husemann Acrylate contact adhesive materials having tight molecular weight distribution
US6765078B2 (en) 2000-06-20 2004-07-20 Tesa Ag Method for producing polyacrylates
US20050032935A1 (en) * 2001-12-06 2005-02-10 Huntsman Advanced Materials Americas, Inc. Heat-curable resin composition
WO2006027387A1 (de) 2004-09-09 2006-03-16 Tesa Ag Verfahren zur herstellung eines klebebandes mit thermisch vernetzter acrylatschmelzkleber-schicht
DE102006015774A1 (de) 2006-04-04 2007-10-11 Construction Research & Technology Gmbh Zweikomponentiges (wässriges) Hybridreaktivharzsystem, Verfahren zu seiner Herstellung sowie dessen Verwendung
DE102006046368A1 (de) 2006-09-29 2008-04-03 Construction Research & Technology Gmbh Funktionalisiertes Polyurethanharz, Verfahren zu seiner Herstellung sowie dessen Verwendung
US7354499B1 (en) * 2006-12-18 2008-04-08 Zap-Lok Pipeline Systems, Inc. Method for making a lubricating fast setting epoxy composition
EP1978069A1 (de) 2007-04-05 2008-10-08 Tesa AG Thermisch vernetzende Polyacrylate und Verfahren zu deren Herstellung
DE102008027501A1 (de) 2008-06-10 2009-12-17 Tesa Se Haftklebemasse mit verbessertem Abzugsverhalten
US20100137524A1 (en) 2008-11-26 2010-06-03 Tesa Se Thermally Crosslinking Polyacrylates And Process For Their Preparation
CN101724173A (zh) 2008-10-22 2010-06-09 蒂萨公司 热交联聚丙烯酸酯及其制备方法

Patent Citations (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4051195A (en) 1975-12-15 1977-09-27 Celanese Polymer Specialties Company Polyepoxide-polyacrylate ester compositions
US4524104A (en) 1981-08-25 1985-06-18 Sanyo Chemical Industries, Ltd. Adhesive composition and laminates therefrom
US5877261A (en) 1995-07-04 1999-03-02 Beiersdorf Ag Crosslinking of acrylate hot-melt pressure-sensitive adhesives
EP0752435A2 (de) 1995-07-04 1997-01-08 Beiersdorf Aktiengesellschaft Vernetzung von Acrylat-Schmelzhaftklebern
US5945491A (en) 1996-07-10 1999-08-31 Carnegie-Mellon University Preparation of novel homo- and copolymers using atom transfer radical polymerization
US5789487A (en) 1996-07-10 1998-08-04 Carnegie-Mellon University Preparation of novel homo- and copolymers using atom transfer radical polymerization
US5854364A (en) 1996-12-26 1998-12-29 Elf Atochem S.A. Process for the controlled radical polymerization or copolymerization of (meth)acrylic, vinyl, vinylidene and diene monomers, and (co)polymers obtained
US6765078B2 (en) 2000-06-20 2004-07-20 Tesa Ag Method for producing polyacrylates
US20040092685A1 (en) 2000-07-28 2004-05-13 Marc Husemann Acrylate contact adhesive materials having tight molecular weight distribution
EP1311555B1 (de) 2000-07-28 2005-03-30 tesa AG Acrylathaftklebemassen mit enger molekulargewichtsverteilung
US6720399B2 (en) 2001-10-05 2004-04-13 Tesa Ag UV-crosslinkable acrylic hotmelt PSAs with narrow molecular weight distribution
US20050032935A1 (en) * 2001-12-06 2005-02-10 Huntsman Advanced Materials Americas, Inc. Heat-curable resin composition
US20090048398A1 (en) 2004-09-09 2009-02-19 Stephan Zollner Method for producing an adhesive strip comprising a thermally cross-linked acrylate hot-melt adhesive layer
WO2006027387A1 (de) 2004-09-09 2006-03-16 Tesa Ag Verfahren zur herstellung eines klebebandes mit thermisch vernetzter acrylatschmelzkleber-schicht
DE102004044086A1 (de) 2004-09-09 2006-03-16 Tesa Ag Thermisch vernetzte Acrylat-Hotmelts
DE102006015774A1 (de) 2006-04-04 2007-10-11 Construction Research & Technology Gmbh Zweikomponentiges (wässriges) Hybridreaktivharzsystem, Verfahren zu seiner Herstellung sowie dessen Verwendung
US20100285311A1 (en) 2006-04-04 2010-11-11 Norbert Steidl Dual component (aqueous) hybrid reactive resin system, method for production and use thereof
US20090240004A1 (en) 2006-09-29 2009-09-24 Alois Maier Functionalized polyurethane resin, method for the production thereof, and use thereof
DE102006046368A1 (de) 2006-09-29 2008-04-03 Construction Research & Technology Gmbh Funktionalisiertes Polyurethanharz, Verfahren zu seiner Herstellung sowie dessen Verwendung
US7354499B1 (en) * 2006-12-18 2008-04-08 Zap-Lok Pipeline Systems, Inc. Method for making a lubricating fast setting epoxy composition
CN101679822A (zh) 2007-04-05 2010-03-24 蒂萨公司 热交联聚丙烯酸酯及其制备方法
DE102007016950A1 (de) 2007-04-05 2008-10-09 Tesa Ag Thermisch vernetzende Polyacrylate und Verfahren zu deren Herstellung
US20100104864A1 (en) 2007-04-05 2010-04-29 Tesa Se Thermally crosslinking polyacrylates and method for producing the same
EP1978069A1 (de) 2007-04-05 2008-10-08 Tesa AG Thermisch vernetzende Polyacrylate und Verfahren zu deren Herstellung
US8802777B2 (en) 2007-04-05 2014-08-12 Tesa Se Thermally crosslinking polyacrylates and method for producing the same
DE102008027501A1 (de) 2008-06-10 2009-12-17 Tesa Se Haftklebemasse mit verbessertem Abzugsverhalten
US20110129632A1 (en) 2008-06-10 2011-06-02 Tesa Se Pressure-sensitive adhesive composition having an improved release behavior
CN101724173A (zh) 2008-10-22 2010-06-09 蒂萨公司 热交联聚丙烯酸酯及其制备方法
US20140170326A1 (en) 2008-10-22 2014-06-19 Tesa Se Thermally Crosslinking Polyacrylates and Process for their Preparation
US20100137524A1 (en) 2008-11-26 2010-06-03 Tesa Se Thermally Crosslinking Polyacrylates And Process For Their Preparation

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
English language abstract for DE 102004044086 which published Mar. 16, 2006.
English translation of Chinese Office Action for corresponding Application CN 201310020836.3 dated Oct. 30, 2015.
English translation of claims from Chinese Office Action for corresponding Application CN 201310020836.3 dated Oct. 30, 2015.
English translation of Search Report for corresponding Application CN 201310020836.3 dated Oct. 30, 2015.
German Search Report for DE 102012200855.1 dated Aug. 8, 2012.

Also Published As

Publication number Publication date
CN103214773A (zh) 2013-07-24
US20130190460A1 (en) 2013-07-25
CN103214773B (zh) 2017-10-20
JP2013147654A (ja) 2013-08-01
DE102012200855A1 (de) 2013-07-25

Similar Documents

Publication Publication Date Title
US10906997B2 (en) Crosslinker-accelerator system for polyacrylates
US9908953B2 (en) Crosslinker-accelerator system for polyacrylates
CA2677728C (en) Thermally crosslinking polyacrylates and method for producing the same
US10174139B2 (en) Crosslinker-accelerator system for polyacrylates
US20140170326A1 (en) Thermally Crosslinking Polyacrylates and Process for their Preparation
US9505959B2 (en) Thermally crosslinking polyacrylates and process for their preparation
KR102387299B1 (ko) 감압 접착제를 제조하기 위한 조성물
US20150037559A1 (en) Pressure-sensitive adhesive
MX2014009229A (es) Adhesivo sensible a la presion.
KR20130143530A (ko) 열­내성 접착 테이프

Legal Events

Date Code Title Description
AS Assignment

Owner name: TESA SE, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:PRENZEL, ALEXANDER, DR;BAMBERG, SARAH;BESCHMANN, JENNIFER;AND OTHERS;SIGNING DATES FROM 20130124 TO 20130128;REEL/FRAME:030011/0524

AS Assignment

Owner name: TESA SE, GERMANY

Free format text: CHANGE OF ADDRESS;ASSIGNOR:TESA SE;REEL/FRAME:037317/0675

Effective date: 20150422

STCF Information on status: patent grant

Free format text: PATENTED CASE

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4